KR102058902B1 - Laminated film, organic electroluminescence device, photoelectric converter, and liquid crystal display - Google Patents

Abstract

The present invention comprises a substrate and at least one thin film layer formed on at least one surface of the substrate,
At least one of the thin film layers contains a silicon atom, an oxygen atom and a carbon atom,
Silicon distribution curve and oxygen distribution respectively showing the relationship between the distance from the surface of the thin film layer in the film thickness direction of the thin film layer, the atomic ratio of silicon contained in the thin film layer at the distance position, the atomic ratio of oxygen and the atomic ratio of carbon, respectively. Curves and carbon distribution curves, all of the specified conditions are met,
The average value of the atomic ratio of carbon calculated | required from a carbon distribution curve is 11at% or more and 21at% or less,
The laminated | multilayer film which can maintain high gas barrier property at the time of bending which the average density of a thin film layer is 2.0 g / cm <^3> or more is provided.

Description

Laminated film, organic electroluminescent device, photoelectric conversion device and liquid crystal display {LAMINATED FILM, ORGANIC ELECTROLUMINESCENCE DEVICE, PHOTOELECTRIC CONVERTER, AND LIQUID CRYSTAL DISPLAY}

The present invention relates to a laminated film having gas barrier properties. Moreover, it is related with the organic electroluminescent apparatus, photoelectric conversion apparatus, and liquid crystal display which have such a laminated film.

The gas barrier film can be suitably used as a packaging container suitable for filling packaging of articles such as food and drink, cosmetics, and detergents. In recent years, a laminated film having a gas barrier property (hereinafter, referred to as "a plastic film") is formed by laminating a thin film made of a material such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide or the like on one surface of the substrate. Laminated film "may be referred to).

As a method of depositing such an inorganic thin film on the surface of a plastic substrate, chemical vapor phases such as vacuum vapor deposition, sputtering, ion plating, etc., physical vapor growth methods (PVD), reduced pressure chemical vapor growth methods, plasma chemical vapor growth methods, etc. Growth method (CVD) is known. For example, Patent Document 1 discloses a laminated film containing silicon, oxygen, and carbon, and having a thin film layer having an average value of carbon atomic ratios of 10.8 at% or less.

Japanese Patent Publication No. 2011-73430

Generally, in the laminated | multilayer film which has gas barrier property, when it bends, there exists a problem that the thin film layer which ensures gas barrier property will fall, and gas barrier property will fall, and when it bends, gas barrier property can be maintained high. Laminated film was desired.

This invention is made | formed in view of such a situation, and an object of this invention is to provide the laminated | multilayer film which can maintain a high gas barrier property even if it curves. Moreover, it aims at providing an organic electroluminescent device, a photoelectric conversion device, and a liquid crystal display which have such a laminated film.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, one aspect of this invention is equipped with a base material and at least 1 thin film layer formed in at least one surface of the said base material, At least 1 layer of the said thin film layers is a silicon atom, an oxygen atom, and a carbon atom. And a ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the thin film layer at the position of the distance, from the surface of the thin film layer in the film thickness direction of the thin film layer. In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, respectively, showing the relationship between the atomic ratio of silicon, the ratio of the number of oxygen atoms (the atomic number of oxygen), and the ratio of the number of carbon atoms (the atomic ratio of carbon), The following conditions (i)-(iii):

(i) the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon satisfy the conditions represented by the following formula (1) in the region of 90% or more in the film thickness direction of the thin film layer;

(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (One)

(ii) the carbon distribution curve has at least one extreme value,

(iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

The present invention satisfies all of the above, and provides an laminated film having an average value of atomic ratios of the carbons obtained from the carbon distribution curve of 11 at% or more and 21 at% or less and an average density of the thin film layer of 2.0 g / cm ³ or more.

In one aspect of the present invention, the thin film layer further contains a hydrogen atom, and is based on the abundance of silicon atoms having different bonding states with oxygen atoms, which are obtained in ²⁹ Si solid NMR measurement of the thin film layer, Q ^4. to that of the peak area, the sum of the peak areas of Q ^1, Q ^2, Q ³ value ratio, satisfy the following condition formula (I) are preferred.

(Value obtained by adding the peak areas of Q ¹ , Q ² and Q ³ ) / (peak area of Q ⁴ ) <1.0. (I)

(Q ¹ represents a silicon atom bonded to one neutral oxygen atom and three hydroxyl groups, Q ² represents a silicon atom bonded to two neutral oxygen atoms and two hydroxyl groups, and Q ³ represents three neutral oxygen atoms and one Represents a silicon atom bonded to a hydroxyl group, and Q ⁴ represents a silicon atom bonded to four neutral oxygen atoms.)

In one aspect of the present invention, the carbon obtained from a carbon oxygen distribution curve showing a relationship between the distance and the ratio of the total number of carbon atoms and oxygen atoms to the total number (atom ratio of carbon and oxygen) And it is preferable that the average value of the atomic ratio of oxygen is 63.7 at% or more and 70.0 at% or less.

In one aspect of the present invention, in the silicon distribution curve, the position where the atomic ratio of the silicon represents a value of 29 at% or more and 38 at% or less occupies 90% or more of the region in the film thickness direction of the thin film layer. desirable.

In one aspect of the present invention, the carbon distribution curve preferably has a plurality of extreme values, and the absolute value of the difference between the maximum value of the extreme value and the minimum value of the extreme value is preferably 15 at% or more.

In one aspect of the present invention, it is preferable that the carbon distribution curve has three or more extreme values, and in the three consecutive extreme values in the carbon distribution curve, the distances between adjacent extreme values are all 200 nm or less. Do.

In one aspect of the present invention, it is preferable that the oxygen distribution curve has three or more extreme values, and in the three successive extreme values in the oxygen distribution curve, the distances between adjacent extreme values are all 200 nm or less. Do.

In one aspect of the present invention, the thin film layer preferably further contains a hydrogen atom.

In one aspect of the present invention, the film thickness of the thin film layer is preferably 5 nm or more and 3000 nm or less.

In 1 aspect of this invention, it is preferable that the said base material consists of at least 1 sort (s) of resin chosen from the group which consists of polyester resin and polyolefin resin.

In one aspect of the present invention, the polyester resin is preferably at least one resin selected from the group consisting of polyethylene terephthalate and polyethylene naphthalate.

One aspect of the present invention provides an organic electroluminescent device comprising the laminate film described above.

One aspect of the present invention provides a photoelectric conversion device including the laminate film described above.

One aspect of the present invention provides a liquid crystal display comprising the laminated film described above.

According to this invention, the laminated | multilayer film which can maintain a high gas barrier property even if it curves can be provided. Moreover, the organic electroluminescent device, photoelectric conversion device, and liquid crystal display which have such a laminated film can be provided.

1: is a schematic diagram which shows the example of the laminated | multilayer film of this embodiment.
It is a schematic diagram which shows an example of the manufacturing apparatus used for manufacture of a laminated | multilayer film.
It is explanatory drawing of the method of calculating film-forming conditions at the time of manufacture of the laminated | multilayer film of this embodiment.
4 is an explanatory diagram for explaining a method for calculating film formation conditions at the time of manufacturing the laminated film of the present embodiment.
5 is a side cross-sectional view of the organic electroluminescent device of the present embodiment.
6 is a side cross-sectional view of the photoelectric conversion device of the present embodiment.
7 is a side cross-sectional view of the liquid crystal display of this embodiment.
8 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 1 obtained in Example 1. FIG.
9 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 2 obtained in Comparative Example 1. FIG.
10 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 3 obtained in Comparative Example 2. FIG.
11 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 4 obtained in Comparative Example 3. FIG.
12 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 5 obtained in Comparative Example 4. FIG.
FIG. 13 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 6 obtained in Example 2. FIG.
14 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 7 obtained in Example 3. FIG.
FIG. 15 is a graph showing a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve of the thin film layer of the laminated film 8 obtained in Example 4. FIG.

[Laminated film]

The laminated | multilayer film of this embodiment is equipped with a base material and at least 1 thin film layer formed in at least one surface of the said base material, At least 1 layer of the said thin film layers contains a silicon atom, an oxygen atom, and a carbon atom, Ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms contained in the thin film layer at the position of the distance and the distance from the surface of the thin film layer in the film thickness direction (atom ratio of silicon), In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve which respectively show the relationship between the ratio of the number of oxygen atoms (atom ratio of oxygen) and the ratio of the number of carbon atoms (atom ratio of carbon), the following conditions (i) to ( iii):

(i) the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon satisfy the conditions represented by the following formula (1) in the region of 90% or more in the film thickness direction of the thin film layer;

(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (One)

(ii) the carbon distribution curve has at least one extreme value,

(iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

Are satisfied, the average value of the atomic ratio of the carbon obtained from the carbon distribution curve is 11 at% or more and 21 at% or less, and the average density of the thin film layer is 2.0 g / cm ³ or more.

Moreover, in the laminated | multilayer film of this embodiment, the thin film layer H may contain the hydrogen atom.

Hereinafter, the laminated | multilayer film which concerns on this embodiment is demonstrated, referring drawings. In addition, in all the following drawings, in order to make drawing clear, a dimension, a ratio, etc. of each component differ suitably.

1: is a schematic diagram about an example of the laminated | multilayer film of this embodiment. In the laminated | multilayer film of this embodiment, the thin film layer H which ensures gas barrier property is laminated | stacked on the surface of the base material F. FIG. In the thin film layer H, at least one layer of the thin film layer H contains silicon, oxygen, and hydrogen, and includes a first layer Ha containing a large amount of SiO ₂ generated by a complete oxidation reaction of a film forming gas described later, The second layer Hb containing a large amount of SiO _x C _y generated by the incomplete oxidation reaction is included, and the first layer Ha and the second layer Hb are alternately stacked.

However, the figure schematically shows that there is a distribution in the film composition, and in reality, the interface is not clearly generated between the first layer Ha and the second layer Hb, but the composition is continuously It is changing. The thin film layer H may be laminated in plural units with the three-layer structure as one unit. The manufacturing method of the laminated | multilayer film shown in FIG. 1 is explained later.

(materials)

The base material F with which the laminated | multilayer film of this embodiment is equipped is a film which has flexibility and uses a polymeric material as a forming material.

When the laminated | multilayer film of this embodiment has a light transmittance, the formation material of base material F is polyester resin, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); Polyolefin resins such as polyethylene (PE), polypropylene (PP), and cyclic polyolefins; Polyamide resins; Polycarbonate resins; Polystyrene resins; Polyvinyl alcohol resin; Saponified products of ethylene-vinyl acetate copolymers; Polyacrylonitrile resins; Acetal resins; And polyimide resins. Among these resins, polyester resins or polyolefin resins are preferred from the viewpoint of high heat resistance and low linear expansion coefficient, and PET or PEN which is a polyester resin is more preferable. Moreover, these resin can be used individually by 1 type or in combination of 2 or more types.

Moreover, when the light transmittance of laminated | multilayer film is not important, it can also be used as a base material F as a composite material which added the filler and the additive to the said resin, for example.

Although the thickness of the base material F is set suitably in consideration of stability, etc. at the time of manufacturing laminated | multilayer film, since conveyance of a base material is easy also in vacuum, it is preferable that it is 5 micrometers-500 micrometers. In addition, when forming the thin film layer H employ | adopted in this embodiment using the plasma chemical vapor deposition method (plasma CVD method), since it discharges through the base material F, the thickness of the base material F is 50 micrometers. It is more preferable that it is -200 micrometers, and it is especially preferable that it is 50 micrometers-100 micrometers.

Moreover, in order to improve the adhesive force with the thin film layer to form, the base material F may perform surface activation treatment for cleaning a surface. Examples of such surface activation treatment include corona treatment, plasma treatment, and frame treatment.

(Thin layer)

The thin film layer H with which the laminated | multilayer film of this embodiment is equipped is a layer formed in the at least single side | surface of the base material F, and at least 1 layer contains silicon, oxygen, and carbon. Moreover, the thin film layer H may contain nitrogen and aluminum further. In addition, the thin film layer H may be formed in both surfaces of the base material F. FIG.

(Density of thin layer)

The thin film layer H with which the laminated | multilayer film of this embodiment is equipped has an average density of 2.0 g / cm <^3> or more high density. In addition, in this specification, the "average density" of the thin film layer H refers to the density calculated | required by the method as described in the "measurement of the average density of (5) thin film layer and the ratio of the number of hydrogen atoms."

Since the thin film layer H has a density of 2.0 g / cm ³ or more, the laminated film of the present embodiment shows high gas barrier property. When the thin film layer H consists of silicon, oxygen, carbon, and hydrogen, the average density of the thin film layer is less than 2.22 g / cm ³ .

(Distribution of Silicon, Carbon, Oxygen in Thin Film Layer)

Moreover, the thin film layer H with which the laminated | multilayer film of this embodiment is equipped has the distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H, the silicon atom of the position of the distance, an oxygen atom, and the like. Silicon distribution showing the relationship between the ratio of the number of silicon atoms (number of atoms of silicon) to the total number of carbon atoms, the ratio of number of oxygen atoms (number of atoms of oxygen) and the ratio of number of carbon atoms (number of atoms of carbon), respectively. In the curve, oxygen distribution curve and carbon distribution curve, all of the above conditions (i) to (iii) are satisfied.

Hereinafter, the distribution curve of each element is demonstrated first, and then, conditions (i)-(iii) are demonstrated.

The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve to be described later use the measurement of X-ray photoelectron spectroscopy (XPS) and rare gas ion sputters such as argon in combination. It can create by performing what is called XPS depth profile measurement which performs surface composition analysis sequentially, exposing.

The distribution curve obtained by XPS depth profile measurement is calculated | required as the atomic ratio (unit: at%) of an element on a vertical axis, and an etching time on a horizontal axis. In measuring the XPS depth profile, it is preferable to adopt a rare gas ion sputtering method using argon (Ar ⁺ ) as the etching ion species, and to set the etching rate (etching rate) to 0.05 nm / sec (SiO ₂ thermal oxide film conversion value). Do.

However, SiO _x C _y is included much in the second layer, since the etching speed than the SiO ₂ thermal oxide film, the SiO ₂ etching rate of a thermal oxide film 0.05nm / sec is used as the basis of etching conditions. That is, the product of 0.05 nm / sec which is an etching rate and the etching time to the base material F does not represent the distance from the surface of the thin film layer H to the base material F strictly.

Therefore, the film thickness of the thin film layer H is measured and obtained separately, and from the obtained film thickness and the etching time from the surface of the thin film layer H to the base material F, the etching time is determined in the "film thickness direction of the thin film layer H". "Distance from the surface of the thin film layer H" corresponds.

Thus, the vertical axis represents the atomic ratio (unit: at%) of each element, and the horizontal axis represents the distance (unit: nm) from the surface of the thin film layer H in the film thickness direction of the thin film layer H. Distribution curves can be created.

First, the film thickness of the thin film layer H is calculated | required by TEM observation of the cross section of the slice of the thin film layer produced by FIB (Focused Ion Beam) process.

Next, from the obtained film thickness and the etching time from the surface of the thin film layer H to the base material F, the "distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H" is determined by the etching time. Match it.

In the XPS depth profile measurement, the carbon atom ratio measured is measured when the etching region is moved from the thin film layer H containing SiO ₂ or SiO _x C _y as a forming material to the base material F containing a polymer material. Increase sharply Therefore, in the present invention, the time when the inclination becomes the maximum in the region in which the "carbon atom ratio increases rapidly" of the XPS depth profile is determined by the thin film layer (H) and the substrate (F) in the XPS depth profile measurement. It is set as the etching time corresponding to the boundary of and.

When the XPS depth profile measurement is performed discretely with respect to the etching time, the time at which the difference between the measured values of the carbon atom ratios at the two adjacent measurement times becomes maximum is extracted, and the intermediate point of the two points is extracted. It is set as the etching time corresponding to the boundary of the thin film layer H and the base material F. FIG.

Moreover, when XPS depth profile measurement is performed continuously with respect to a film thickness direction, the time derivative of the graph of carbon atom ratio with respect to etching time is the largest in the said "carbon atom ratio rapidly increasing" area | region. Let it be set to the etching time corresponding to the boundary of the thin film layer H and the base material F. FIG.

That is, by making the film thickness of the thin film layer which the cross section of the slice of the thin film layer calculated | required from TEM observation correspond to "the etching time corresponding to the boundary of the thin film layer H and the base material F" in the said XPS depth profile, The distribution curve of each element can be created which makes the atomic ratio of an element and the horizontal axis the distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H.

In the condition (i) of the thin film layer H, the thin film layer H has the following formula (a) in the region where the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon are 90% or more of the thickness of the layer. 1).

(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (One)

It is preferable that thin film layer H satisfy | fills said Formula (1) in 95% or more of area | regions of the film thickness of thin film layer H, and satisfy | fills it in 100% area | region of the film thickness of thin film layer (H). Particularly preferred.

When the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon in the thin film layer H satisfy the conditions of (i), the gas barrier property of the laminated film obtained becomes sufficient.

In condition (ii) of the thin film layer H, the thin film layer H has a carbon distribution curve having at least one extreme value.

In the thin film layer H, it is more preferable that the carbon distribution curve has at least two extremes, and particularly preferably has at least three extremes. When the carbon distribution curve does not have an extreme value, when the resulting laminated film is bent, the gas barrier property is lowered and becomes insufficient.

In the case of having at least three extreme values in this manner, from the surface of the thin film layer H in the film thickness direction of the thin film layer H at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value, It is preferable that all the absolute values of the difference of the distance of are 200 nm or less, and it is more preferable that it is 100 nm or less.

In addition, in this specification, "extreme value" means the maximum or minimum value of the atomic ratio of elements with respect to the distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H in the distribution curve of each element. Say.

In addition, in this specification, "maximum value" is a point where the value of the atomic ratio of an element changes from an increase to a decrease when the distance from the surface of the thin film layer H is changed, and the value of the atomic ratio of the element of the point From this point of view, the value of the atomic ratio of the element at the position where the distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H is further changed by 20 nm is reduced by 3 at% or more.

In addition, in this embodiment, "minimum value" is a point where the value of the atomic ratio of an element changes from a decrease to an increase, when the distance from the surface of the thin film layer H is changed, and also the atomic ratio of the element of that point is changed. The value of the atomic ratio of the element of the position which changed the distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H further 20 nm from the point from that point increases 3 at% or more.

In condition (iii) of the thin film layer H, the thin film layer H is one in which the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.

In the thin film layer H, the absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon is more preferably 6 at% or more, and particularly preferably 7 at% or more. If the absolute value is less than 5 at%, the gas barrier property when the laminated film obtained is bent is insufficient.

(Atomic ratio of carbon in the thin film layer)

Moreover, the average value of the atomic ratio of carbon calculated | required from the carbon distribution curve of the thin film layer H with which the laminated | multilayer film of this embodiment is equipped is 11 at% or more and 21 at% or less.

In this specification, the "average value of the atomic ratio of carbon calculated | required from a carbon distribution curve" employ | adopted the value which averaged the atomic ratio of carbon contained in the area | region between the following two points.

First, in the laminated film of the present embodiment, the thin film first layer (Ha), the second layer (Hb), which contains a lot of SiO _x C _y to (H) is, contains a lot of SiO ₂ in the film thickness direction, A layer structure called one layer (Ha) is formed. For this reason, in a carbon distribution curve, it is anticipated to have the minimum value of the carbon atom ratio corresponding to 1st layer Ha in the film surface vicinity and the base material F vicinity.

Therefore, in the case where the carbon distribution curve has such a minimum value, the above average value is determined from the minimum value at the surface side (origin side) of the thin film layer in the carbon distribution curve. The average value of the atomic ratio of carbon contained in the area | region to the minimum before moving to the "increase" area | region was employ | adopted.

Moreover, in the laminated | multilayer film of the other structure used as the comparison object of the laminated | multilayer film of this embodiment, one or both of a surface side and a base material side may not have the minimum as mentioned above. For this reason, when a carbon distribution curve does not have such a minimum value, the reference point which calculates an average value is calculated | required as follows on the surface side and the base material side of the thin film layer H.

On the surface side, in the area | region where the value of carbon atom ratio is decreasing when the distance from the surface of the thin film layer H is changed, the predetermined thickness (first point) and the film thickness of the thin film layer H from the said point The second point when the absolute value of the difference in the value of the carbon atomic ratio with the point (second point) in which the distance from the surface of the thin film layer H in the direction is further changed by 20 nm is 5 at% or less as the reference point. did.

Moreover, on the base material side, the value of carbon atom ratio when the distance from the surface of the thin film layer H is changed in the vicinity of the area | region where the carbon atom ratio increases rapidly which is the area | region containing the boundary of a thin film layer and a base material. In this increasing area, a predetermined point (first point) and the point from which the distance from the surface of the thin film layer H in the film thickness direction of the thin film layer H are further changed by 20 nm (second point) The 1st point was made into the reference | standard point when the absolute value of the difference of the value of carbon atom ratio with the dot) becomes 5 at% or less.

The "average" of the atomic ratio of carbon is determined by arithmetical averaging each measurement value when the XPS depth profile measurement in the preparation of the carbon distribution curve is performed discretely with respect to the film thickness direction. In addition, when XPS depth profile measurement is performed continuously with respect to the film thickness direction, the integral value of the carbon distribution curve in the area | region which averages is calculated | required, and the area | region corresponded to an integral value with the length of the said area | region as one side. It is obtained by calculating the other side of the rectangle having.

If the average value of the atomic ratio of carbon in the thin film layer H is 11at% or more and 21at% or less, it becomes possible to maintain high gas barrier property even after bending a laminated | multilayer film. 11at% or more and 20at% or less are preferable, and, as for this average value, 11at% or more and 19.5at% or less are more preferable.

In addition, when the laminated film has transparency, when the difference between the refractive index of the base material of the laminated film and the refractive index of the thin film layer is large, reflection and scattering may occur at the interface between the base material and the thin film layer, and there is a fear that the transparency is lowered. In this case, the transparency of a laminated film can be improved by preparing the atomic ratio of carbon of a thin film layer within the said numerical range, and making small the refractive index difference between a base material and a thin film layer.

For example, when using PEN as a base material, if the average value of the atomic ratio of carbon is 11 at% or more and 21 at% or less, the light transmittance of a laminated film is high compared with the case where the average value of the atomic number ratio of carbon is larger than 21 at%. It becomes what has favorable transparency.

Moreover, in the laminated | multilayer film of this embodiment, it is preferable that the average value of the atomic ratio of carbon and oxygen calculated | required from a carbon-oxygen distribution curve is 63.7 at% or more and 70.0 at% or less.

In the present specification, the "average value of the atomic ratio of carbon and oxygen" is similar to the "average value of the atomic ratio of carbon" described above, from the minimum value at the surface side (origin side) of the thin film layer in the carbon distribution curve. In a distribution curve, the value which carried out the arithmetic mean of the atomic ratio of carbon and oxygen contained in the area | region to the minimum value before moving to the area | region of a base material was employ | adopted.

Moreover, in the laminated | multilayer film of this embodiment, in the silicon distribution curve, the position where the atomic ratio of silicon shows the value of 29at% or more and 38at% or less occupies 90% or more of area | regions in the film thickness direction of a thin film layer. desirable. When the atomic ratio of silicon is contained in this range, there exists a tendency for the gas barrier property of the laminated | multilayer film obtained to improve. Moreover, it is more preferable that the position where the atomic ratio of silicon shows the value of 30at% or more and 36at% or less in a silicon distribution curve occupies 90% or more area | region in the film thickness direction of a thin film layer.

At this time, the ratio of the distance from the surface of the thin film layer in the film thickness direction of the thin film layer and the total number of oxygen atoms and carbon atoms to the total number of silicon atoms, oxygen atoms and carbon atoms at the position of the distance (oxygen and In the oxygen carbon distribution curve showing the relationship with the atomic ratio of carbon), the position where the atomic ratio of oxygen and carbon shows a value of 62 at% or more and 71 at% or less is 90% or more in the film thickness direction of the thin film layer. It is desirable to occupy.

Moreover, in the laminated | multilayer film of this embodiment, it is preferable that a carbon distribution curve has some extreme value, and the absolute value of the difference of the maximum value of an extreme value and the minimum value of an extreme value is 15 at% or more.

Moreover, in the laminated | multilayer film of this embodiment, since the gas barrier property at the time of bending the laminated | multilayer film obtained is improved, it is preferable that an oxygen distribution curve has at least 1 extreme value, and it is more preferable to have at least 2 extreme values. It is preferred, and it is particularly preferable to have at least three extremes.

In addition, in the case of having at least three extreme values in this way, from the surface of the thin film layer H in the film thickness direction of the thin film layer H in the one extreme value of the oxygen distribution curve and the extreme value adjacent to the extreme value, It is preferable that all the absolute values of the difference of the distance of are 200 nm or less, and it is more preferable that it is 100 nm or less.

Moreover, in the laminated | multilayer film of this embodiment, since the gas barrier property in the case of bending the laminated | multilayer film obtained is improved, the difference of the maximum value and the minimum value of the atomic ratio of oxygen in the oxygen distribution curve of the thin film layer H It is preferable that absolute value is 5 at% or more, It is more preferable that it is 6 at% or more, It is especially preferable that it is 7 at% or more.

In the laminated | multilayer film of this embodiment, since the gas barrier property in the case where the laminated | multilayer film obtained is bent is improved, the difference of the maximum value and the minimum value with respect to the atomic ratio of silicon in the silicon distribution curve of the thin film layer H is improved. It is preferable that an absolute value is less than 5 at%, It is more preferable that it is less than 4 at%, It is especially preferable that it is less than 3 at%.

Moreover, in the laminated | multilayer film of this embodiment, since the gas barrier property in the case of bending the laminated | multilayer film obtained is improved, the difference of the maximum value and the minimum value with respect to the atomic ratio of oxygen and carbon in an oxygen carbon distribution curve It is preferable that an absolute value is less than 5 at%, It is more preferable that it is less than 4 at%, It is especially preferable that it is less than 3 at%.

Moreover, in the laminated | multilayer film of this embodiment, the thin film layer H is parallel to the surface of the film surface direction (thin film layer H) from a viewpoint of forming the thin film layer H which is uniform and excellent gas barrier property in the whole film surface. Substantially the same in one direction). In the present specification, the fact that the thin film layer H is substantially the same in the film surface direction means that an oxygen distribution curve, a carbon distribution curve and an arbitrary two measurement points on the film surface of the thin film layer H are measured by XPS depth profile measurement. In the case of producing an oxygen carbon distribution curve, the number of extremes of the carbon distribution curve obtained at two arbitrary measurement points is the same, and the difference between the maximum value and the minimum value of the atomic ratio of carbon in each carbon distribution curve is the same. Absolute values are the same or within 5 at% of difference.

In addition, in the laminated | multilayer film of this embodiment, it is preferable that a carbon distribution curve is substantially continuous. In the present specification, that the carbon distribution curve is substantially continuous means that the atomic ratio of carbon in the carbon distribution curve does not include a portion that changes discontinuously, specifically, the film thickness of the thin film layer H In the relation between the distance (x, unit: nm) from the surface of the layer in the direction and the atomic ratio of carbon (C, unit: at%), the following formula (F1):

| dC / dx | ≦ 0.5... (F1)

It means to meet the conditions shown.

( ²⁹ Si-solid NMR peak area)

In addition, the thin film layer (H) having the laminated film of the present embodiment, at least one layer contains silicon, oxygen, and hydrogen, obtained according to solid ²⁹ Si- NMR measurement of the thin film layer (H), the Q ⁴ for the peak areas, Q ^1, Q ^2, it is preferable that a sum of the peak areas of Q ³ value ratio, satisfy the following condition (I).

(Value obtained by adding the peak areas of Q ¹ , Q ² and Q ³ ) / (peak area of Q ⁴ ) <1.0. (I)

Here, Q ^1, Q ^2, Q ^3, Q ⁴ are, it indicates to a silicon atom constituting the thin film layer (H), distinguished by the nature of the oxygen bonded to the silicon atom. That is, each symbol of Q ¹ , Q ² , Q ³ , Q ⁴ has an oxygen atom bonded to the silicon atom when the oxygen atom forming the Si—O—Si bond is a “neutral” oxygen atom with respect to the hydroxyl group. It is the same as that.

Q ¹ : a silicon atom bonded to one neutral oxygen atom and three hydroxyl groups

Q ² : Silicon atoms bonded to two neutral oxygen atoms and two hydroxyl groups

Q ³ : Silicon atoms bonded to three neutral oxygen atoms and one hydroxyl group

Q ⁴ : Silicon atom bonded to 4 neutral oxygen atoms

Here, when measuring " ²⁹ Si-solid NMR of a thin film layer (H)", the base material F may be contained in the test piece used for a measurement.

The peak area of solid NMR can be computed as follows, for example.

First, the spectrum obtained by ²⁹ Si-solid NMR measurement is smoothed. Specifically, the spectrum obtained by ²⁹ Si-solid NMR measurement is Fourier-transformed, the high frequency of 100 Hz or more is removed, and the smoothing process is performed by inverse Fourier-transformation (low pass filter process). ^The spectrum obtained by ²⁹ Si-solid NMR measurement includes noise of a frequency higher than that of the peak signal, but the noise is removed by the low pass filter processing.

In the following description, the spectrum after smoothing is called "a measurement spectrum."

Next, the measurement spectrum is separated into each peak of Q ¹ , Q ² , Q ³ and Q ⁴ . In other words, assume that the peaks of Q ¹ , Q ² , Q ³ , and Q ⁴ represent Gaussian distribution (normal distribution) curves centered on inherent chemical shifts, respectively, and Q ¹ , Q ² , Q ³ , and Q ^4. The parameters such as the height and the half value width of each peak are optimized so that the model spectrum obtained by summation matches with the one after the smoothing of the measurement spectrum.

The parameter is optimized by using an iterative method. In other words, the iterative method is used to calculate a parameter in which the sum of squares of deviations between the model spectrum and the measurement spectrum converges to a local minimum.

Next, each peak area is calculated by integrating the peaks of Q ¹ , Q ² , Q ³ , and Q ⁴ thus obtained, respectively. Using the peak area thus obtained, the left side of the above-mentioned formula (I) (the sum of the peak areas of Q ¹ , Q ² , and Q ³ ) / (peak area of Q ⁴ ) is obtained, and as an evaluation index of gas barrier property. I use it.

It is preferable that the laminated | multilayer film of this embodiment is a silicon atom of Q <^4> or more among the silicon atoms which comprise the thin film layer (H) quantified by solid NMR measurement.

The silicon atom of Q ⁴ is surrounded by four neutral oxygen atoms around the silicon atom, and the four neutral oxygen atoms combine with the silicon atom to form a network structure. On the other hand, since the silicon atoms of Q ¹ , Q ² and Q ³ are bonded to one or more hydroxyl groups, fine pores in which covalent bonds are not formed between adjacent silicon atoms exist. Thus, the more silicon atom of Q ^4, the thin film layer (H) is a dense layer, it may be laminated to the film to achieve high gas barrier property.

In the laminated film of the present embodiment, when the above equation as shown in (I), (Q ^1, Q ^2, a total of the peak areas of Q ³ value) / (peak area of Q ⁴⁾ is less than 1.0, high gas It is preferable because it shows barrier property.

The value of (peak area of ^{Q 4) (Q 1, Q} 2, Q ³ of a total peak area value) / silver, and more preferably 0.8 or less, more preferably 0.6 or less.

In addition, when using the material containing a silicone resin or glass as the base material F, in order to avoid the influence of the silicon in the base material in solid NMR measurement, the thin film layer H is isolate | separated from the base material F, and the thin film layer ( What is necessary is just to measure the solid NMR of only silicon contained in H).

As a method of separating thin film layer H and base material F, the method of scraping thin film layer H with a metal spatula etc., and extract | collecting to the sample tube in solid NMR measurement is mentioned, for example. Moreover, you may remove the base material F using the solvent which melt | dissolves only a base material, and may collect the thin film layer H which remains as a residue.

In the laminated | multilayer film of this embodiment, it is preferable that the film thickness of the thin film layer H is the range of 5 nm or more and 3000 nm or less, It is more preferable that it is the range of 10 nm or more and 2000 nm or less, It is especially preferable that it is the range of 100 nm or more and 1000 nm or less. Do. When the film thickness of the thin film layer H is 5 nm or more, gas barrier properties, such as oxygen gas barrier property and water vapor barrier property, further improve. Moreover, by being 3000 nm or less, the higher effect which suppresses the fall of the gas barrier property at the time of bending is obtained.

Moreover, the laminated | multilayer film of this embodiment contains (a) a silicon atom, an oxygen atom, and a carbon atom, (b) average density is 2.0 g / cm <^3> or more, (c) said conditions (i)-(iii) ), And (d) at least one thin film layer (H) having an average atomic ratio of carbon determined from the carbon distribution curve of 11 at% or more and 21 at% or less, but satisfies all of the conditions (a) to (d). Two or more thin film layers may be provided. In addition, when providing two or more such thin film layers H, the material of several thin film layers H may be the same, and may differ. Moreover, when providing two or more such thin film layers H, this thin film layer H may be formed on one surface of the base material F, and may be formed on both surfaces of the base material F. As shown in FIG. In addition, the plurality of thin film layers H may include the thin film layer H which does not necessarily have gas barrier properties.

Moreover, when the laminated | multilayer film of this embodiment has the layer which laminated | stacked two or more thin film layers H, the total value (film thickness of the barrier film which laminated | stacked thin film layer H) the film thickness of thin film layer H is 100 nm. It is larger and it is preferable that it is 3000 nm or less. When the total value of the film thicknesses of the thin film layer H is 100 nm or more, gas barrier properties such as oxygen gas barrier property and water vapor barrier property are further improved. Moreover, when the total value of the film thickness of the thin film layer H is 3000 nm or less, the higher effect which suppresses the fall of the gas barrier property at the time of bending is obtained. And it is preferable that the film thickness per layer of the thin film layer H is larger than 50 nm.

(Other configurations)

Although the laminated | multilayer film of this embodiment is equipped with the base material F and the thin film layer H, you may further provide the primer coating layer, a heat sealable resin layer, an adhesive bond layer, etc. as needed. Such a primer coating layer can be formed using a well-known primer coating agent which can improve adhesiveness with a laminated | multilayer film. Moreover, such a heat sealable resin layer can be formed using a well-known heat sealable resin suitably. Moreover, such an adhesive bond layer can be formed suitably using a well-known adhesive agent, and you may adhere | attach some laminated | multilayer film by such an adhesive bond layer.

The laminated | multilayer film of this embodiment is comprised as mentioned above.

(Manufacturing method of laminated film)

Next, the manufacturing method of the laminated | multilayer film which has a thin film layer which satisfy | fills all the conditions (a)-(d) mentioned above is demonstrated.

FIG. 2: is a figure which shows an example of the manufacturing apparatus of the laminated | multilayer film which concerns on this embodiment, and is a schematic diagram of the apparatus which forms a thin film layer by a plasma chemical vapor deposition method. In addition, in FIG. 2, in order to make drawing clear, a dimension, a ratio, etc. of each component are varied suitably.

The manufacturing apparatus 10 shown in the figure has a delivery roll 11, a winding roll 12, conveyance rolls 13-16, the 1st film-forming roll 17, the 2nd film-forming roll 18, and the gas supply pipe 19. ), The magnetic field forming apparatus 23 provided inside the plasma generating power supply 20, the electrode 21, the electrode 22, the first film forming roll 17, and the second film forming roll 18. The magnetic field forming device 24 is provided.

Among the components of the manufacturing apparatus 10, the first film forming roll 17, the second film forming roll 18, the gas supply pipe 19, the magnetic field forming apparatus 23, and the magnetic field forming apparatus 24 are laminated films. In manufacturing, it is placed in a vacuum chamber (not shown). This vacuum chamber is connected to a vacuum pump (not shown). The pressure inside the vacuum chamber is adjusted by the operation of the vacuum pump.

By using this apparatus, the film forming gas supplied from the gas supply pipe 19 is supplied to the space between the first film forming roll 17 and the second film forming roll 18 by controlling the plasma generation power supply 20. A discharge plasma can be generated, and plasma CVD film formation can be performed by a continuous film formation process using the generated discharge plasma.

The delivery roll 11 is provided in the state in which the base material F before film-forming is wound up, and it sends out, unwinding the base material F in a long direction. Moreover, the winding roll 12 is provided in the edge part side of the base material F, it winds up, pulling up the base material F after film-forming is carried out, and is accommodated in roll shape.

The 1st film-forming roll 17 and the 2nd film-forming roll 18 are extended in parallel and opposingly arranged. Both rolls are formed of an electroconductive material and convey the base material F while rotating, respectively. It is preferable to use the same diameter as the 1st film-forming roll 17 and the 2nd film-forming roll 18, For example, it is preferable to use the thing of 5 cm or more and 100 cm or less.

The first film forming roll 17 and the second film forming roll 18 are insulated from each other and are connected to a common plasma generation power supply 20. When an AC voltage is applied from the plasma generation power supply 20, the electric field is formed in the space SP between the first film forming roll 17 and the second film forming roll 18. It is preferable that the plasma generation power supply 20 can apply the applied electric power to 100W-10kW, and can make the frequency of alternating current 50Hz-500kHz.

The magnetic field forming apparatus 23 and the magnetic field forming apparatus 24 are members which form a magnetic field in the space SP, and are stored inside the first film forming roll 17 and the second film forming roll 18. The magnetic field forming apparatus 23 and the magnetic field forming apparatus 24 are fixed so as not to rotate together with the first film forming roll 17 and the second film forming roll 18 (that is, the relative posture to the vacuum chamber does not change). It is.

The magnetic field forming apparatus 23 and the magnetic field forming apparatus 24 include the center magnets 23a and 24a extending in the same direction as the extending direction of the first film forming rolls 17 and the second film forming rolls 18, and the center magnets. It surrounds around 23a, 24a, and has the annular outer magnet 23b, 24b extended in the same direction as the extending direction of the 1st film-forming roll 17 and the 2nd film-forming roll 18. As shown in FIG. In the magnetic field forming apparatus 23, a magnetic force line (magnetic field) connecting the central magnet 23a and the external magnet 23b forms an endless tunnel. Similarly, in the magnetic field forming device 24, the magnetic force lines connecting the central magnet 24a and the external magnet 24b form an endless tunnel.

The discharge plasma of the film forming gas is generated by the magnetron discharge in which the electric field formed between the magnetic lines of force and the first film forming roll 17 and the second film forming roll 18 intersects. Discharge plasma of the deposition gas is generated. That is, as will be described later in detail, the space SP is used as a film forming space for performing plasma CVD film formation and is not in contact with the first film forming roll 17 and the second film forming roll 18 in the substrate F. On the non-surface (film formation surface), a thin film layer in which the deposition gas is deposited via the plasma state is formed.

In the vicinity of the space SP, a gas supply pipe 19 for supplying the film forming gas G such as a source gas of plasma CVD to the space SP is provided. The gas supply pipe 19 has a tubular shape extending in the same direction as the extending direction of the first film forming rolls 17 and the second film forming rolls 18, and is provided in the space SP from the openings provided in plural places. The deposition gas G is supplied. In the figure, the state which supplies the film-forming gas G toward the space SP from the gas supply pipe 19 is shown by the arrow.

The source gas can be appropriately selected and used depending on the material of the barrier film to be formed. As the source gas, for example, an organosilicon compound containing silicon can be used. Examples of such organosilicon compounds include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, Diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane, Dimethyldisilazane, trimethyldisilazane, tetramethyldisilazane, pentamethyldisilazane, and hexamethyldisilazane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of the handleability of the compound and the gas barrier property of the barrier film to be obtained. Moreover, these organosilicon compounds can be used individually by 1 type or in combination of 2 or more types. Moreover, you may use as a source gas as a silicon source of the barrier film formed by containing monosilane other than the organosilicon compound mentioned above.

As the film forming gas, a reaction gas may be used in addition to the source gas. As such a reaction gas, the gas which reacts with source gas and becomes inorganic compounds, such as an oxide and a nitride, can be selected suitably and can be used. As a reaction gas for forming an oxide, oxygen and ozone can be used, for example. Moreover, as a reaction gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used individually by 1 type or in combination of 2 or more types. For example, when forming an oxynitride, the reaction gas for forming an oxide and the reaction gas for forming a nitride are combined, Can be used.

In order to supply source gas into a vacuum chamber, film-forming gas may contain carrier gas as needed. In addition, as film-forming gas, in order to generate discharge plasma, you may use gas for discharge as needed. As such a carrier gas and a gas for discharge, a well-known thing can be used suitably, For example, Rare gases, such as helium, argon, neon, xenon; Hydrogen may be used.

Although the pressure (vacuum degree) in a vacuum chamber can be adjusted suitably according to the kind of source gas, etc., it is preferable that the pressure of space SP is 0.1 Pa-50 Pa. When plasma CVD is made into the low pressure plasma CVD method for the purpose of suppressing gaseous-phase reaction, it is 0.1Pa-10Pa normally. Moreover, although the electric power of the electrode drum of a plasma generating apparatus can be suitably adjusted according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable that they are 0.1 kW-10 kW.

Although the conveyance speed (line speed) of the base material F can be adjusted suitably according to the kind of source gas, the pressure in a vacuum chamber, etc., it is preferable that it is 0.1 m / min-100 m / min, and 0.5 m / min-20 m / min It is more preferable that is. If the line speed is less than the lower limit, wrinkles due to heat tends to occur in the base material F. On the other hand, if the line speed exceeds the upper limit, the film thickness of the barrier film formed tends to be thin.

In the manufacturing apparatus 10 as described above, film formation is performed on the substrate F as follows.

First, before the film formation, pretreatment may be performed so that the outgas generated from the base material F is sufficiently reduced. The amount of outgas generated from the base material F can be determined using the pressure when the base material F is attached to the manufacturing apparatus and the pressure inside the device (in the chamber) is reduced. For example, if the pressure in the chamber of a manufacturing apparatus is 1x10 <^-3> Pa or less, it can be judged that the generation amount of the outgas from the base material F is sufficiently small.

As a method of reducing the generation amount of the outgas from the base material F, the drying method by vacuum drying, heat drying, a combination thereof, and natural drying is mentioned. In any of the drying methods, in order to promote the drying of the inside of the substrate F wound in a roll shape, the rolls are unwound (winding and winding) repeatedly during drying to expose the entire substrate F under a dry environment. It is preferable.

Vacuum drying is performed by putting the base material (F) in a pressure resistant vacuum container, evacuating the inside of a vacuum container using a pressure reducer like a vacuum pump, and making it into a vacuum. 1000 Pa or less is preferable, as for the pressure in the vacuum container at the time of vacuum drying, 100 Pa or less is more preferable, 10 Pa or less is further more preferable. The evacuation of the vacuum vessel may be performed continuously by continuously operating the pressure reducer, or may be performed intermittently by operating the pressure reducer intermittently while managing the internal pressure not to be constant or higher. It is preferable that drying time is 8 hours or more, It is more preferable that it is 1 week or more, It is more preferable that it is 1 month or more.

Heat drying is performed by exposing the base material F to 50 degreeC or more environment. 50 degreeC or more and 200 degrees C or less are preferable, and 70 degreeC or more and 150 degrees C or less of heating temperature are more preferable. At the temperature over 200 degreeC, there exists a possibility that the base material F may deform | transform. Moreover, when an oligomer component elutes from the base material F and precipitates on a surface, there exists a possibility that a defect may arise. Drying time can be suitably selected according to heating temperature or the heating means to be used.

As a heating means, if the base material F can be heated to 50 degreeC or more and 200 degrees C or less under normal pressure, it will not specifically limit. Among the known devices, infrared heaters, microwave heaters and heating drums are preferably used.

Here, the infrared heater is an apparatus for heating an object by radiating infrared rays from the infrared ray generating means.

A microwave heating apparatus is an apparatus which heats an object by irradiating a microwave from a microwave generating means.

A heating drum is an apparatus which heats a drum surface and heats it by heat conduction from a contact part by making an object contact a drum surface.

Natural drying is performed by arranging the base material F in a low humidity atmosphere, and maintaining a low humidity atmosphere by ventilating dry gas (dry air, dry nitrogen). When performing natural drying, it is preferable to arrange | position a drying agent, such as a silica gel, in the low-humidity environment in which the base material F is arrange | positioned. It is preferable that drying time is 8 hours or more, It is more preferable that it is 1 week or more, It is more preferable that it is 1 month or more.

These drying may be performed separately before attaching the base material F to a manufacturing apparatus, or may be performed in a manufacturing apparatus after attaching the base material F to a manufacturing apparatus.

As a method of drying after attaching the base material F to a manufacturing apparatus, the inside of a chamber is depressurized, sending out and conveying the base material F from a delivery roll. Moreover, it is good also as a roll made to pass through having a heater, and heating a roll, using it as a heating drum mentioned above, and heating.

As another method of reducing the outgas from the base material F, an inorganic film is formed into a film on the surface of the base material F beforehand. Examples of the method for forming the inorganic film include physical deposition methods such as vacuum deposition (heat deposition), electron beam (EB) deposition, sputtering, and ion plating. The inorganic film may be formed by chemical deposition such as thermal CVD, plasma CVD, atmospheric pressure CVD, or the like. Moreover, you may further reduce the influence of outgas by performing the drying process by the above-mentioned drying method to the base material F which formed the inorganic film into the surface.

Subsequently, the inside of the vacuum chamber (not shown) is set to a reduced pressure environment, and is applied to the first film forming roll 17 and the second film forming roll 18 to generate an electric field in the space SP.

At this time, since the magnetic field forming apparatus 23 and the magnetic field forming apparatus 24 form the endless tunnel-like magnetic field described above, the deposition gas is introduced to the electrons emitted to the magnetic field and the space SP. As a result, a discharge plasma of the donut-shaped film forming gas along the tunnel is formed. Since this discharge plasma can be generated at a low pressure around several Pa, the temperature in the vacuum chamber can be set at around room temperature.

On the other hand, since the temperature of the electrons trapped at high density in the magnetic field formed by the magnetic field forming device 23 and the magnetic field forming device 24 is high, a discharge plasma generated by the collision between the electrons and the film forming gas is generated. That is, electrons are trapped in the space SP by the magnetic field and the electric field formed in the space SP, thereby forming a high-density discharge plasma in the space SP. More specifically, a high density (high intensity) discharge plasma is formed in the space overlapping with the endless tunnel-shaped magnetic field, and low density (low intensity) in the space not overlapping with the endless tunnel-shaped magnetic field. Of) a discharge plasma is formed. The intensity of these discharge plasmas changes continuously.

When the discharge plasma is generated, a large amount of radicals or ions are generated to cause a plasma reaction to proceed, and a reaction between the source gas and the reactive gas included in the deposition gas occurs. For example, the organosilicon compound which is a source gas and oxygen which is a reaction gas react, and the oxidation reaction of an organosilicon compound arises. Here, in the space in which the high-strength discharge plasma is formed, the reaction tends to proceed because of the large amount of energy applied to the oxidation reaction, and mainly the complete oxidation reaction of the organosilicon compound can be generated. On the other hand, in a space where a low intensity discharge plasma is formed, the reaction is less likely to proceed because of less energy applied to the oxidation reaction, and mainly an incomplete oxidation reaction of the organosilicon compound can be generated.

In the present specification, the reaction with a "complete oxidation of the organic silicon compound" is an organic silicon compound and oxygen proceeds, indicate that the organic silicon compound to be oxidized and decomposed to silicon dioxide (SiO ₂₎ with water and carbon dioxide .

For example, when the film forming gas contains hexamethyldisiloxane (HMDSO: (CH ₃ ) ₆ Si ₂ O) which is a raw material gas and oxygen (O ₂ ) which is a reaction gas, the following reaction formula The reaction as described in (1) takes place, and silicon dioxide is produced.

[Tue 1]

(CH ₃ ) ₆ Si ₂ O + 12O ₂ → 6CO ₂ + 9H ₂ O + 2SiO ₂ . (One)

In the present specification, "incomplete oxidation of the organic silicon compound" is, not the complete oxidation of organic silicon _{compound, SiO x C y (0 <} x <2, 0 including the carbon in the structure, not the SiO ₂ It indicates that <y <2) becomes a reaction that occurs.

In the manufacturing apparatus 10 as described above, since the discharge plasma is formed on the surfaces of the first film forming roll 17 and the second film forming roll 18 in a donut shape, the first film forming roll 17 and the second film forming roll are formed. The base material F which conveys the surface of 18 passes through the space in which the high intensity discharge plasma is formed, and the space in which the low intensity discharge plasma is formed, alternately. For this reason, the surface of the base material F passing through the surfaces of the first film forming roll 17 and the second film forming roll 18 contains a large amount of SiO ₂ generated by a complete oxidation reaction (the first film of FIG. 1). In one layer Ha, a layer (second layer Hb in FIG. 1) containing a large amount of SiO _x C _y generated by an incomplete oxidation reaction is sandwiched and formed.

In addition, high-temperature secondary electrons are prevented from flowing into the base material F by the action of the magnetic field. Therefore, high electric power can be supplied while the temperature of the base material F is kept low, and high-speed film formation is achieved. . The deposition of the film mainly occurs only on the film formation surface of the base material F, and the film roll is hardly covered and contaminated, so that stable film formation for a long time is possible.

Next, the method of controlling the average value of the atomic ratio of carbon in a thin film layer is demonstrated.

In order to make the average value of the atomic ratio of carbon contained in a thin film layer with respect to the thin film layer formed using the above-mentioned apparatus, 11at% or more and 21at% or less, For example, source gas and reaction gas are made into the range determined as follows. The film is formed using the mixed film forming gas.

3 is a graph showing an average value of the atomic ratio of carbon contained in the thin film layer with respect to the amount of source gas. In the graph of the figure, the horizontal axis shows the amount of raw material gas (sccm: Standard Cubic Centimeter per Minute), and the vertical axis shows the average value of the atomic ratio of carbon (unit at%), using HMDSO as the source gas and oxygen as the reaction gas. The relationship in the case of using is shown.

Fig. 3 is a graph showing the relationship of the average value of the atomic ratio of carbon to the amount of HMDSO when the amount of oxygen is fixed at 250 sccm, and the graph of HMDSO when the amount of oxygen is fixed at 500 sccm. The graph (represented by the code | symbol O2) which shows the relationship of the average value of the atomic ratio of carbon with respect to quantity is shown. In the graph of FIG. 3, after measuring and plotting the average value of the atomic ratio of carbon with respect to three points which changed the quantity of HMDSO in each oxygen amount, each point was curve-regressed by the spline curve.

In addition, film-forming conditions other than the quantity of oxygen and HMDSO are as follows.

(Film forming condition)

Vacuum degree in the vacuum chamber: 3Pa

Applied Power from Plasma Generation Power Supply: 0.8kW

Frequency of plasma generation power supply: 70 kHz

Conveying speed of film: 0.5m / min

From the graph of FIG. 3 (1), the following can be said qualitatively.

First, when the flow rate of oxygen is constant, increasing the flow rate of HMDSO increases the average value of the atomic ratio of carbon in the thin film layer. This can be explained by increasing the amount of carbon contained in the thin film layer as a result of the reaction conditions under which HMDSO is incompletely oxidized because the amount of HMDSO increases relative to the amount of oxygen.

If the flow rate of HMDSO is constant, increasing the flow rate of oxygen decreases the average value of the atomic ratio of carbon in the thin film layer. Since the amount of HMDSO decreases relative to the amount of oxygen, this can be explained as the amount of carbon contained in the thin film layer is reduced as a result of approaching the reaction condition under which HMDSO is completely oxidized.

Moreover, even if the ratio of HMDSO and oxygen is the same, if the total amount of deposition gas is large, the average value of the atomic ratio of carbon in the thin film layer increases. This can be explained by increasing the amount of carbon contained in the thin film layer as a result of the reaction conditions under which HMDSO performs incomplete oxidation because the energy obtained from the discharge plasma is relatively reduced when the flow rate of the entire deposition gas is large.

FIG. 3 (2) is a partially enlarged view of the graph shown in FIG. 3 (1) and is a graph in which the vertical axis is set to 11 at% or more and 21 at% or less. From the coordinates of the contact point X1 between the graph O1 in FIG. 3 (2) and the horizontal axis below, the flow rate of HMDSO when the average value of the atomic ratio of carbon is 11at% under the condition of the flow rate of oxygen at 250 sccm. It can be seen that this is about 33 sccm. From the contact point X2 between the graph O1 and the horizontal axis above, it can be seen that under the condition of a flow rate of oxygen of 250 sccm, the flow rate of HMDSO when the average value of the atomic ratio of carbon is 21 at% is about 55 sccm. have. That is, under the conditions of the flow rate of oxygen of 250 sccm, it can be seen that the average value of the atomic ratio of carbon can be 11 at% or more and 21 at% or less when the flow rate of HMDSO is about 33 sccm to about 55 sccm.

Similarly, from the coordinates of the contacts X3 and X4 between the graph O2 and the upper and lower horizontal axes, under the condition of the flow rate of oxygen of 500 sccm, the flow rate of HMDSO for the average value of the atomic ratio of carbon to be 11 at% or more and 21 at% or less. The upper limit value and the lower limit value can be read, and it can be seen that they are about 51 sccm and about 95 sccm, respectively.

4 is a graph obtained by converting the flow rate of HMDSO on the horizontal axis and the flow rate of oxygen on the vertical axis with respect to the relationship between the flow rate of HMDSO and the flow rate of oxygen obtained from the points X1 to X4 shown in FIG. 3. In FIG. 4, area | region AR enclosed by the line segment when it connects with a line segment in order of code | symbol X1, X2, X4, X3, X1 is HMDSO of which the average value of the atomic ratio of carbon becomes 11 at% or more and 21 at% or less. The flow rate and the flow rate of oxygen are shown. That is, when plotted in FIG. 4, the average value of the atomic ratio of carbon of the thin film layer obtained can be 11 at% or more and 21 at% or less by controlling and forming into a quantity contained in area | region AR the flow volume of HMDSO and oxygen.

In the above description, the oxygen flow rates 250 sccm and 500 sccm are exemplified as conditions, but, of course, the relationship between the flow rate of HMDSO and the flow rate of oxygen when the oxygen flow rate is less than 250 sccm or more than 500 sccm is performed by performing the same operation. You can get it.

In this way, it is possible to control the amounts of HMDSO and oxygen to determine the reaction conditions to form a thin film layer having an average value of carbon atoms in the atomic ratio of 11 at% or more and 21 at% or less.

In the above description, the graphs were plotted and plotted for three points in which the amount of HMDSO was changed for each oxygen flow rate. However, even if the level in which the amount of HMDSO was changed for oxygen flow rate was two points, the atomic ratio of carbon of the two points was When the average value of each is less than 11 at% and larger than 21 at%, you may create the graph corresponded to FIG. 3 from the result of the said 2 points | pieces. Of course, you may produce the graph corresponded to FIG. 3 from the result of four or more points.

In addition, after fixing the amount of film-forming gas, the atomic ratio of carbon with respect to the change of the said voltage at the time of changing the applied voltage applied to the 1st film-forming roll 17 and the 2nd film-forming roll 18, for example. It is also possible to obtain the relationship of the average value of and to obtain the applied voltage which is the average value of the atomic ratio of the desired carbon, as described above.

Thus, the film-forming conditions are prescribed | regulated, the thin film layer is formed in the surface of a base material by the plasma CVD method using discharge plasma, and the laminated | multilayer film of this embodiment can be manufactured.

Moreover, in the laminated | multilayer film of this embodiment, the average density of the thin film layer formed is 2.0 g / cm <^3> or more.

In the thin film layer, it can be considered that the layer containing much SiO _x C _y generated by the incomplete oxidation reaction has a structure in which oxygen atoms are substituted with carbon atoms from a network structure of SiO ₂ (density: 2.22 g / cm ³ ). Can be. In a layer containing a large amount of SiO _x C _y , the bond length of the sp3 bond of Si-O (if the average value of the atomic ratio of carbon in the thin film layer is large) as long as the oxygen atom of SiO ₂ is substituted with many carbon atoms ( The average density of the thin film layer decreases because the molecular volume increases from the difference in the bond length (about 1.86 kPa) of the sp3 bond of Si-C). However, when the average value of the atomic ratio of carbon of the thin film layer is 11 at% or more and 21 at% or less, the average density of the thin film layer is 2.0 g / cm ³ or more.

According to the laminated | multilayer film of this embodiment which satisfy | fills the conditions (a)-(d) as mentioned above, it can be set as the laminated | multilayer film which can maintain high gas barrier property even if it bends.

[Organic EL Device]

5 is a side cross-sectional view showing a structural example of an organic electroluminescence (organic EL) device of the present embodiment.

The organic EL device according to the present embodiment is applicable to various electronic devices using light. The organic EL device of the present embodiment may be, for example, a part of a display unit such as a mobile device or a part of an image forming device such as a printer. The organic EL device of the present embodiment may be, for example, a light source (backlight) such as a liquid crystal display panel, or may be, for example, a light source of an illuminator.

The organic EL device 50 shown in FIG. 5 includes a first electrode 52, a second electrode 53, a light emitting layer 54, a laminated film 55, a laminated film 56, and a sealing material 65. have. The laminated | multilayer film of this embodiment mentioned above is used for laminated | multilayer film 55 and 56, the laminated | multilayer film 55 is equipped with the base material 57 and the barrier film 58, and the laminated | multilayer film 56 is a base material 59 and a barrier film 60 are provided.

The light emitting layer 54 is disposed between the first electrode 52 and the second electrode 53, and the first electrode 52, the second electrode 53, and the light emitting layer 54 form an organic EL element. Forming. The laminated film 55 is disposed on the side opposite to the light emitting layer 54 with respect to the first electrode 52. The laminated film 56 is arrange | positioned on the opposite side to the light emitting layer 54 with respect to the 2nd electrode 53. As shown in FIG. In addition, the laminated | multilayer film 55 and the laminated | stacked film 56 are bonded by the sealing material 65 arrange | positioned so that the periphery of an organic EL element may be formed, and the sealing film which seals an organic EL element inside is formed.

In the organic EL device 50, when electric power is supplied between the first electrode 52 and the second electrode 53, carriers (electrons and holes) are supplied to the light emitting layer 54, and the light emitting layer 54 is provided. There is light on. The power supply source to the organic EL device 50 may be mounted in the same device as the organic EL device 50, or may be provided outside the device. The light generated from the light emitting layer 54 is used for displaying, forming or illuminating an image according to the use of the device including the organic EL device 50 and the like.

In the organic EL device 50 of the present embodiment, a commonly known material is used as the material for forming the first electrode 52, the second electrode 53, and the light emitting layer 54 (the material for forming the organic EL element). . In general, it is known that the material for forming an organic EL device is easily deteriorated by moisture or oxygen, but in the organic EL device 50 of the present embodiment, the laminate of the present embodiment can maintain high gas barrier properties even when bent. The organic EL element is sealed in a sealing structure surrounded by the films 55 and 56 and the sealing material 65. For this reason, even if it bends, there is little performance deterioration and it can be set as the highly reliable organic electroluminescent apparatus 50.

In addition, in the organic EL device 50 of this embodiment, it demonstrated as using the laminated films 55 and 56 of this embodiment, but either of the laminated films 55 and 56 has the gas barrier property which has a different structure. It may be a substrate.

[Liquid Crystal Display]

6 is a side sectional view of a liquid crystal display according to the present embodiment.

The liquid crystal display 100 shown in the figure includes a first substrate 102, a second substrate 103, and a liquid crystal layer 104. The first substrate 102 is disposed to face the second substrate 103. The liquid crystal layer 104 is disposed between the first substrate 102 and the second substrate 103. In the liquid crystal display 100, for example, the first substrate 102 and the second substrate 103 are bonded together using the sealing material 130, and the first substrate 102 and the second substrate 103 are bonded to each other. And the liquid crystal layer 104 is enclosed in a space surrounded by the sealing material 130.

The liquid crystal display 100 has a plurality of pixels. The plurality of pixels are arranged in a matrix. The liquid crystal display 100 of this embodiment can display a full color image. Each pixel of the liquid crystal display 100 includes a sub pixel Pr, a sub pixel Pg, and a sub pixel Pb. The light blocking area BM is provided between the sub pixels. The three sub-pixels emit color light having different gray levels corresponding to the image signal to the display side of the image. In this embodiment, red light is emitted from the sub-pixel Pr, green light is emitted from the sub-pixel Pg, and blue light is emitted from the sub-pixel Pb. Three colors of color light emitted from three sub-pixels are mixed and visually recognized, thereby displaying one pixel in full color.

The first substrate 102 includes a laminated film 105, an element layer 106, a plurality of pixel electrodes 107, an alignment film 108, and a polarizing plate 109. The pixel electrode 107 forms a pair of electrodes with the common electrode 114 mentioned later. The laminated film 105 is equipped with the base material 110 and the barrier film 111. The base material 110 is a thin plate shape or a film shape. The barrier film 111 is formed on one side of the substrate 110. The element layer 106 is laminated on the base 110 on which the barrier film 111 is formed. The plurality of pixel electrodes 107 are independently provided for each sub pixel of the liquid crystal display 100 on the element layer 106. The alignment film 108 is provided on the pixel electrode 107 and between the pixel electrodes 107 over the plurality of sub pixels.

The second substrate 103 provides the laminated film 112, the color filter 113, the common electrode 114, the alignment film 115, and the polarizing plate 116. The laminated film 112 is equipped with the base material 117 and the barrier film 118. The base material 117 is thin plate shape or film shape. The barrier film 118 is formed on one side of the substrate 117. The color filter 113 is laminated | stacked and formed on the base material 110 in which the barrier film 111 was formed. The common electrode 114 is provided on the color filter 113. The alignment film 115 is provided on the common electrode 114.

The first substrate 102 and the second substrate 103 are disposed to face each other with the pixel electrode 107 and the common electrode 114 facing each other, and are bonded to each other with the liquid crystal layer 104 sandwiched therebetween. The pixel electrode 107, the common electrode 114, and the liquid crystal layer 104 form a liquid crystal display element. Moreover, the laminated | multilayer film 105 and the laminated | multilayer film 112 cooperate with the sealing material 130 arrange | positioned so that the circumference | surroundings of a liquid crystal display element may be formed, and the sealing structure which seals a liquid crystal display element inside is formed.

In such a liquid crystal display 100, since the laminated | multilayer film 105 and the laminated | multilayer film 112 of this embodiment with high gas barrier property form a part of the sealing structure which seals a liquid crystal display element inside, it curves. Even if it is made, there is little possibility that a liquid crystal display element may deteriorate with oxygen and moisture in air, and performance may fall, and it can be set as the highly reliable liquid crystal display 100. FIG.

In addition, in the liquid crystal display 100 of this embodiment, it demonstrated as using the laminated films 105 and 112 of this embodiment, but either of the laminated films 105 and 112 has a gas barrier substrate with a different structure. It may be.

[Photoelectric conversion device]

7 is a side cross-sectional view of the photoelectric conversion device of the present embodiment. The photoelectric conversion device of the present embodiment can be used in various devices for converting light energy into electrical energy, such as photodetecting sensors and solar cells.

The photoelectric conversion apparatus 400 shown in the figure includes a first electrode 402, a second electrode 403, a photoelectric conversion layer 404, a laminated film 405, and a laminated film 406. The laminated film 405 includes a substrate 407 and a barrier film 408. The laminated film 406 includes a substrate 409 and a barrier film 410. The photoelectric conversion layer 404 is disposed between the first electrode 402 and the second electrode 403, and the first electrode 402, the second electrode 403, and the photoelectric conversion layer 404 are A photoelectric conversion element is formed.

The laminated film 405 is disposed on the side opposite to the photoelectric conversion layer 404 with respect to the first electrode 402. The laminated film 406 is disposed on the side opposite to the photoelectric conversion layer 404 with respect to the second electrode 403. In addition, the laminated | multilayer film 405 and the laminated | multilayer film 406 are joined by the sealing material 420 arrange | positioned so that the circumference | surroundings of a photoelectric conversion element may be formed, and the sealing structure which seals a photoelectric conversion element inside is formed.

In the photoelectric conversion device 400, the first electrode 402 is a transparent electrode, and the second electrode 403 is a reflective electrode. In the photoelectric conversion device 400 of the present example, the light energy of light incident through the first electrode 402 to the photoelectric conversion layer 404 is converted into electrical energy in the photoelectric conversion layer 404. This electric energy is taken out of the photoelectric conversion apparatus 400 through the 1st electrode 402 and the 2nd electrode 403. FIG. The material etc. are selected suitably so that each component arrange | positioned at the optical path of the light which injects into the photoelectric conversion layer 404 from the outside of the photoelectric conversion apparatus 400 may have a light transmittance. The components disposed other than the optical path of the light from the photoelectric conversion layer 404 may be a translucent material or may be a material that blocks some or all of the light.

In the photoelectric conversion device 400 of the present embodiment, a commonly known material is used as the first electrode 402, the second electrode 403, and the photoelectric conversion layer 404. In the photoelectric conversion apparatus 400 of this embodiment, the photoelectric conversion element is sealed by the sealing structure enclosed by the laminated films 405 and 406 and the sealing material 420 of this embodiment with high gas barrier property. For this reason, even if it bends, there is little possibility that a photoelectric conversion layer or an electrode will deteriorate with oxygen and moisture in air, and performance will fall, and it can be set as the highly reliable photoelectric conversion apparatus 400.

In addition, in the photoelectric conversion apparatus 400 of this embodiment, it demonstrated as sandwiching a photoelectric conversion element with the laminated | multilayer films 405 and 406 of this embodiment, but either of the laminated | multilayer films 405 and 406 is another structure. A gas barrier substrate may be provided.

As mentioned above, although the preferred embodiment which concerns on this invention was described referring an accompanying drawing, it goes without saying that this invention is not limited to this example. The formulation form, the combination, etc. of each structural member shown in the above-mentioned example are an example, and can be variously changed based on a design request etc. in the range which does not deviate from the main point of this invention.

Example

Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example. In addition, the measured value with respect to the laminated | multilayer film employ | adopted the value measured by the following method.

[How to measure]

(1) Measurement of water vapor permeability

The water vapor transmission rate of a laminated film is measured using the water vapor permeability measuring instrument (GTR Tech-30 make, GTR tech-30 XASC) on conditions of temperature 40 degreeC, the humidity 0% RH of the low humidity side, and the humidity 90% RH of the high humidity side. did.

In addition, the detection limit of the measuring instrument used by "(1) Measurement of water vapor permeability" is 1x10 <^-4> g / (m <^2> * day).

(2) Measurement of water vapor transmission rate after bending test

First, the bending test of the laminated | multilayer film was performed by returning the laminated | multilayer film which is a measurement object to a flat cylindrical rod made of metal, leaving it to stand for 1 minute, and then returning it flat. The radius of curvature R in the bending test corresponds to the radius of the rod winding the laminated film. However, when the number of turns of the laminated film increases, the curvature is half of the diameter to the outer circumference of the film when the film is wound. It was set as the radius R.

The water vapor permeability of the laminated film after the bending test is based on the temperature of 40 ° C., the humidity of 10% RH on the low humidity side, and the humidity of 100% RH on the high humidity side with respect to the laminated film after the bending test. Lyssy-L80-5000).

In addition, the detection limit of the measuring instrument used by "(2) Measurement of the water vapor transmission rate after a bending test" is 2x10 <^-2> g / (m <^2> * day).

About the laminated | multilayer film which performs a bending test, it confirmed that it had the water vapor transmittance below a detection limit in the measurement by the same measuring device before a bending test. Whether or not the laminated film was able to detect water vapor permeability after the bending test, the presence or absence of a decrease in gas barrier property due to the bending test was confirmed.

"(1) Measurement of water vapor permeability" "(2) Measurement of water vapor permeability after bending test", all in accordance with JIS K 7129: 2008 "Calculation method of plastic film and sheet water vapor permeability (device measurement method)" Annex C "Gas It measured according to "the method of calculating the water vapor permeability according to the chromatography method" (hereinafter sometimes referred to as JIS gas chromatography method).

(3) Measurement of film thickness of thin film layer

The film thickness of a thin film layer was calculated | required by observing the cross section of the slice of the thin film layer produced by FIB (Focused Ion Beam) processing using the transmission electron microscope (made by Hitachi, Ltd., HF-2000).

(FIB condition)

Apparatus: SMI-3050 (manufactured by SII)

Acceleration voltage: 30 kV

(4) Distribution curve of each element of thin film layer

With respect to the thin film layer of the laminated film, the distribution curves of silicon atoms, oxygen atoms, and carbon atoms are measured by XPS depth profile under the following conditions, and the horizontal axis is the distance (nm) from the surface of the thin film layer and the vertical axis is the atomic percentage of each element. Was created by graphing.

(Measuring conditions)

Etching Ion Species: Argon (Ar ⁺ )

Etching Rate (SiO ₂ Thermal Oxidation Equivalent): 0.05 nm / sec

Etching Interval (SiO ₂ Thermal Oxidation Value): 10nm

X-ray photoelectron spectroscopy: manufactured by Thermo Fisher Scientific, VG Theta Probe

Irradiation X-ray: Single Crystal Spectroscopy AlKα

Spot shape and spot diameter of X-ray: oval of 800 x 400 μm.

(5) measurement of light transmittance

Measurement of the light transmittance spectrum of the laminated film was performed according to JIS R1635 using an ultraviolet visible near infrared spectrophotometer (JASCO Corporation, trade name Jasco V-670), and the visible light transmittance at a wavelength of 550 nm was measured. It was set as the light transmittance of a laminated film.

(Measuring conditions)

Integral sphere: None

Measurement wavelength range: 190 to 2700 nm

Spectrum Width: 1nm

Wavelength Scan Rate: 2000nm / min

Response: Fast

(6) Measurement of average density of thin film layer and ratio of number of hydrogen atoms

The measurement of the average density of the thin film layer and the measurement of the ratio of the number of hydrogen atoms (confirmation of the presence of hydrogen atoms) are carried out by Rutherford Backscattering Spectrometry (RBS) and Hydrogen Forward scattering Spectrometry (HFS). Done.

The RBS method and the HFS method were measured using the following common measuring apparatus.

(Measuring device)

Accelerator: National Electrostatics Corp (NEC) Accelerator

Instrument: Ends manufactured by Evans

(i.RBS measurement)

An RBS spectrum was obtained by injecting a He ion beam into the thin film layer of the laminated film from the normal direction of the surface of the thin film layer and detecting the energy of He ions scattered backward with respect to the incident direction.

(Analysis condition)

He ⁺⁺ ion beam energy: 2.275 MeV

RBS detection angle: 160 °

Grazing Angle with respect to the ion beam incident direction: about 115 °

Analysis Mode: RR (Rotation Random)

(ii.HFS method measurement)

About the thin film layer of laminated | multilayer film, the energy of hydrogen which injects a He ion beam from the direction of 75 degrees with respect to the normal line of the thin film layer surface (the direction of the elevation angle of 15 degrees of the thin film layer surface), and scatters 30 degrees forward with respect to the ion beam incident direction, and By detecting the quantity, HFS spectrum was obtained.

(Analysis condition)

He ⁺⁺ ion beam energy: 2.275 MeV

Detection angle: 160 °

Grazing Angle with respect to the ion beam incident direction: approx. 30 °

The average density of the thin film layer is calculated by calculating the weight of the thin film layer in the measurement range from the number of atoms of silicon, the number of carbon atoms, the number of oxygen atoms, and the number of atoms of hydrogen determined by the HFS method. It calculated | required by dividing by volume (product of ion beam irradiation area and film thickness).

The ratio of the number of hydrogen atoms is the ratio of the number of atoms of hydrogen to the total number of atoms of the number of atoms of silicon, the number of atoms of carbon, the number of atoms of oxygen, and the number of atoms of hydrogen determined by the HFS method (atoms Percentage).

(7) Measurement of ²⁹ Si-solid NMR Spectrum

^{The 29} Si-solid NMR spectrum was measured using a nuclear magnetic resonance apparatus (BRUKER, AVANCE300) under the following conditions.

<Measurement conditions>

Cumulative count: 49152

Relief time: 5 seconds

Resonance Frequency: 59.5815676MHz

MAS rotation: 3 kHz

CP method

Moreover, the peak area of solid NMR was computed as follows. It is known in advance that any of the silicon atoms of Q ³ or Q ⁴ is contained and the silicon atoms of Q ¹ or Q ² are not contained in the thin film layer to be measured in this embodiment.

First, the spectrum obtained by ²⁹ Si-solid NMR measurement was smoothed.

That is, the smoothing process is performed by Fourier transforming the spectrum obtained by ²⁹ Si-solid NMR measurement, removing the high frequency of 100 Hz or more, and performing inverse Fourier transform (low pass filter process). In the following description, the spectrum after smoothing is called "a measurement spectrum."

Next, the measurement spectrum was separated into peaks of Q ³ and Q ⁴ . That is, it is assumed that the peak of Q ^{3 and} the peak of Q ⁴ each represent a Gaussian distribution (normal distribution) curve centered on an inherent chemical shift (Q ³ : -102 ppm, Q ⁴ : -112 ppm), and Q Parameters such as the height and the half value width of each peak were optimized so that the model spectrum in which ³ and Q ⁴ were added matches the one after the smoothing of the measurement spectrum.

For the optimization of the parameters, the iteration method was used so that the sum of the squares of the deviations between the model spectrum and the measurement spectrum converged to the minimum value.

Next, the peaks of Q ³ and Q ⁴ thus obtained and the area of the portion surrounded by the baseline were integrated to determine the peak areas of Q ³ and Q ⁴ . Furthermore, using the calculated peak area, (peak area of Q ³ ) / (peak area of Q ⁴ ) is obtained, the value of (peak area of Q ³ ) / (peak area of Q ⁴ ) and gas barrier properties Confirmed the relationship.

(Example 1)

The laminated film was manufactured using the manufacturing apparatus shown in FIG. 2 mentioned above.

That is, a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 μm, width: 350 mm, manufactured by Teijin DuPont Films Japan Limited, trade name "Teonex Q65FA") It used as the base material (F), and attached this to the delivery roll 11.

Then, a film forming gas (raw material gas (HMDSO) and a reactive gas (oxygen gas) is formed in the space between the first film forming roll 17 and the second film forming roll 18 where an endless tunnel-shaped magnetic field is formed. ) And a power supply to each of the first film forming roll 17 and the second film forming roll 18 to discharge between the first film forming roll 17 and the second film forming roll 18. To form a thin film by the plasma CVD method under the following conditions. The laminated film 1 was obtained by this process.

(Film forming condition)

Supply amount of raw gas: 50sccm

Oxygen gas supply: 250 sccm

Vacuum degree in the vacuum chamber: 3Pa

Applied Power from Plasma Generation Power Supply: 0.8kW

Frequency of plasma generation power supply: 70 kHz

Conveying speed of film: 0.5m / min

When the cross-sectional TEM photograph of the FIB processed section was confirmed about the obtained laminated | multilayer film 1, four layers of different colors (the above two layers are the protective layers provided on the thin film layer at the time of FIB processing, and the two layers below the protective layer) In this order, the thin film layer and the substrate) can be observed.

Moreover, the carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve with respect to the obtained laminated | multilayer film 1 are shown in FIG.

(Comparative Example 1)

The laminated film 2 was obtained like Example 1 except having changed the supply amount of oxygen gas into 500 sccm. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve for the obtained laminated film 2 are shown in FIG. 9.

(Comparative Example 2)

A laminated film 3 was obtained in the same manner as in Example 1 except that the supply amount of the source gas was 100 sccm. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve for the obtained laminated film 3 are shown in FIG. 10.

(Comparative Example 3)

A laminated film 4 was obtained in the same manner as in Example 1 except that the supply amount of the source gas was 25 sccm. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve of the obtained laminated film 4 are shown in FIG.

(Comparative Example 4)

Batch-type plasma CVD apparatus using a biaxially stretched polyethylene naphthalate film (PEN film, thickness: 100 micrometers, size: 165 mm x 170 mm, Teijin Dupont film make, brand name "Tonex Q65FA") as a base material Was used to form a thin film by the plasma CVD method.

HMDSO was used as a source gas and oxygen gas was used as a reaction gas for the film forming gas. The amount of deposition gas supplied was controlled to form HMDSO at 12 sccm and oxygen gas at 68 sccm, to obtain a laminated film 5. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve for the obtained laminated film 5 are shown in FIG. 12.

(Example 2)

The laminated film 6 was obtained like Example 1 except having changed the supply amount of oxygen gas into 400 sccm. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the carbon oxygen distribution curve of the obtained laminated film 6 are shown in FIG. 13.

(Example 3)

The laminated film 7 was obtained like Example 1 except having changed the supply amount of oxygen gas into 450 sccm. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve for the obtained laminated film 7 are shown in FIG. 14.

(Example 4)

The laminated film 8 was obtained like Example 1 except having changed the supply amount of oxygen gas into 480sccm. The carbon distribution curve, the silicon distribution curve, the oxygen distribution curve, and the oxygen distribution curve for the obtained laminated film 8 are shown in FIG. 15.

Each measurement result is shown in Table 1 about the laminated | multilayer film 1-5 of Example 1 and Comparative Examples 1-4. Moreover, each measurement result is shown in Table 2 about the laminated | multilayer films 6-8 of Examples 2-4.

As a result of the evaluation, the laminated films 1 and 6 to 8 of Examples 1 to 4 maintained good gas barrier properties even after the bending test.

On the other hand, the gas-barrier property of the laminated | multilayer films 2-4 of Comparative Examples 1-3 fell by the bending test.

Moreover, the laminated film 5 of the comparative example 4 has a water vapor permeability of 1.3 g / (m <^2> * day), and it turns out that it is a water vapor permeability equivalent to the PEN film of a base material, and the provision of gas barrier property by the formed thin film layer Not recognized.

From these results, it was confirmed that the laminated | multilayer film of this invention can maintain high gas barrier property, even if it is bent. The laminated | multilayer film of this invention can be used suitably for organic electroluminescent apparatus, a photoelectric conversion apparatus, and a liquid crystal display.

This invention is a laminated | multilayer film which can maintain high gas barrier property even if it is bent, Such a laminated | multilayer film can be applied to an organic electroluminescent device, a photoelectric conversion device, and a liquid crystal display, for example.

10 Manufacturing Equipment
11 delivery roll
12 winding rolls
13 ~ 16 conveying roll
17 First Film Roll
18 2nd Tabernacle Roll
20 Plasma Generating Power Supply
23, 24 magnetic field forming device
50 organic electroluminescent devices
100 liquid crystal display
400 photoelectric converter
55, 56, 105, 106, 405, 406 laminated film
F film (base material)
SP space (film formation space)

Claims (14)

A base material and at least one thin film layer formed on at least one surface of the base material,
At least one of the thin film layers contains a silicon atom, an oxygen atom and a carbon atom,
The ratio of the number of silicon atoms to the total number of silicon atoms, oxygen atoms, and carbon atoms contained in the thin film layer at the position of the distance and the distance from the surface of the thin film layer in the film thickness direction of the thin film layer (atom of silicon In the silicon distribution curve, the oxygen distribution curve, and the carbon distribution curve, respectively, showing the relationship between the ratio of the number of oxygen atoms, the ratio of the number of oxygen atoms (the number of atoms of oxygen), and the ratio of the number of carbon atoms (the number of atoms of carbon). ) ~ (iii):
(i) the atomic ratio of silicon, the atomic ratio of oxygen and the atomic ratio of carbon satisfy the conditions represented by the following formula (1) in the region of 90% or more in the film thickness direction of the thin film layer;
(Atomic ratio of oxygen)> (atomic ratio of silicon)> (atomic ratio of carbon) (One)
(ii) the carbon distribution curve has at least one extreme value,
(iii) The absolute value of the difference between the maximum value and the minimum value of the atomic ratio of carbon in the carbon distribution curve is 5 at% or more.
All of them,
The average value of the atomic number ratio of the said carbon calculated | required from the said carbon distribution curve is 11at% or more and 21at% or less,
The laminated film of which the average density of the thin film layer is 2.0 g / cm ³ or more. The method according to claim 1,
The thin film layer further contains a hydrogen atom,
Sum the peak areas of Q ¹ , Q ² , and Q ³ with respect to the peak area of Q ⁴ based on the abundance of silicon atoms having different bonding states with oxygen atoms determined in ²⁹ Si solid NMR measurement of the thin film layer. A laminated film in which the ratio of one value satisfies the following conditional formula (I).
(Value obtained by adding the peak areas of Q ¹ , Q ² and Q ³ ) / (peak area of Q ⁴ ) <1.0. (I)
(Q ¹ represents a silicon atom bonded to one neutral oxygen atom and three hydroxyl groups, Q ² represents a silicon atom bonded to two neutral oxygen atoms and two hydroxyl groups, and Q ³ represents three neutral oxygen atoms and one Represents a silicon atom bonded to a hydroxyl group, and Q ⁴ represents a silicon atom bonded to four neutral oxygen atoms.) The method according to claim 1 or 2,
The average value of the atomic number ratio of carbon and oxygen calculated | required from the carbon-oxygen distribution curve which shows the relationship between the said distance and the ratio (the atomic ratio of carbon and oxygen) of the total number of carbon atoms and oxygen atoms with respect to the said total number The laminated | multilayer film which is 63.7at% or more and 70.0at% or less. The method according to claim 1 or 2,
The said laminated film WHEREIN: The laminated | multilayer film which the position which the atomic ratio of the said silicon shows the value of 29at% or more and 38at% or less occupies 90% or more area | region in the film thickness direction of the said thin film layer. The method according to claim 1 or 2,
The carbon distribution curve has a plurality of extreme values,
The laminated | multilayer film whose absolute value of the difference between the maximum value of the said extreme value and the minimum value of the said extreme value is 15 at% or more. The method according to claim 1 or 2,
The carbon distribution curve has three or more extreme values,
Laminated | multilayer film of all three said extreme values in the said carbon distribution curve WHEREIN: The distance between adjacent extreme values is 200 nm or less in all. The method according to claim 1 or 2,
The oxygen distribution curve has three or more extreme values,
Laminated | multilayer film of all three said extreme values in the said oxygen distribution curve WHEREIN: The distance between adjacent extreme values is 200 nm or less in all. The method according to claim 1 or 2,
The laminated film in which the said thin film layer contains a hydrogen atom further. The method according to claim 1 or 2,
The laminated film whose film thickness of the said thin film layer is 5 nm or more and 3000 nm or less. The method according to claim 1 or 2,
Laminated | multilayer film which the said base material consists of at least 1 sort (s) of resin chosen from the group which consists of polyester resin and polyolefin resin. The method according to claim 10,
The said laminated resin is at least 1 sort (s) of resin chosen from the group which consists of a polyethylene terephthalate and a polyethylene naphthalate. The organic electroluminescent device provided with the laminated | multilayer film of Claim 1 or 2. The photoelectric conversion apparatus provided with the laminated | multilayer film of Claim 1 or 2. The liquid crystal display provided with the laminated | multilayer film of Claim 1 or 2.

Images